JP2005082649A - Slurry for polishing use - Google Patents
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- JP2005082649A JP2005082649A JP2003313842A JP2003313842A JP2005082649A JP 2005082649 A JP2005082649 A JP 2005082649A JP 2003313842 A JP2003313842 A JP 2003313842A JP 2003313842 A JP2003313842 A JP 2003313842A JP 2005082649 A JP2005082649 A JP 2005082649A
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- 238000005498 polishing Methods 0.000 title claims abstract description 151
- 239000002002 slurry Substances 0.000 title claims abstract description 67
- 239000007800 oxidant agent Substances 0.000 claims abstract description 35
- -1 iodate compound Chemical class 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008119 colloidal silica Substances 0.000 claims abstract description 14
- 239000006061 abrasive grain Substances 0.000 claims abstract description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims abstract description 5
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000003617 peroxidasic effect Effects 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 13
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 239000010936 titanium Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000007517 polishing process Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
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- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は、半導体、電子部品の製造工程で使用される研磨用スラリーに関し、例えば、各種の半導体製造過程における基板の薄膜などを研磨するのに供される研磨用スラリーに関する。 The present invention relates to a polishing slurry used in a manufacturing process of a semiconductor or an electronic component, for example, a polishing slurry used for polishing a thin film of a substrate in various semiconductor manufacturing processes.
近年、水系媒体中にシリカ粒子を分散させて形成される研磨用スラリーを用いた化学機械研磨（ＣＭＰ）技術が注目されている。ＣＭＰ技術では、図２に示すように、研磨装置の研磨プレート１上に研磨パッド２を配置し、この研磨パッド２上にノズル６を介して研磨用スラリー３を供給しながら、研磨プレート１とウェハ４とを回転させつつ、ウェハ４上に形成された配線金属や層間絶縁膜等の表面を研磨パッド２上に押し付け、研磨用スラリー３による化学的、物理的研磨作用によって、ウェハ４の配線金属や層間絶縁膜等の表面を研磨し、平坦化する。
In recent years, a chemical mechanical polishing (CMP) technique using a polishing slurry formed by dispersing silica particles in an aqueous medium has attracted attention. In the CMP technique, as shown in FIG. 2, a polishing pad 2 is disposed on a
このような研磨用スラリー３には、機械的研磨性能を上げるため酸化剤を含ませたものが知られている（特許文献１参照）。
ところで、従来の研磨用スラリーの場合、酸化剤が１種類しか含ませられていなかった。したがって、従来においては、ウェハなどにおける配線金属（タングステン、銅、アルミニウムなど）に対して研磨レート（単位時間当たりの研磨速度）が比較的高いものとなっているが、バリア金属（チタン、窒化チタン、タリウム、窒化タリウムなど）に対しては、酸化剤の機能が十分でなく研磨レートが低いものとなっていた。 By the way, in the case of the conventional polishing slurry, only one kind of oxidizing agent was included. Therefore, conventionally, the polishing rate (polishing rate per unit time) is relatively high with respect to the wiring metal (tungsten, copper, aluminum, etc.) in the wafer, but the barrier metal (titanium, titanium nitride). , Thallium, thallium nitride, etc.), the function of the oxidizing agent is not sufficient and the polishing rate is low.
このため、配線金属のみならず、バリア金属を形成したウェハに対する研磨作業を行う場合、一回の研磨工程によって配線金属とともにバリア金属をも研磨することが望ましいのであるが、配線金属層をおもに研磨する工程（一次研磨）と、バリア金属とともに配線金属を研磨する工程（二次研磨）との複数段階に別けて研磨を行うことがあった。そのため、先の研磨と後の研磨とで研磨スラリーを変更調整することがあった。詳述すると、配線金属とバリア金属とでその研磨速度が異なるため、おもに配線金属を研磨除去するときの研磨用スラリーと、おもにバリア金属を研磨するときの研磨用スラリーとで異なる組成の研磨用スラリーを準備して、それぞれの工程に合わせて研磨用スラリーを使い分ける研磨作業を行っていた。 For this reason, when polishing work not only on the wiring metal but also on the wafer on which the barrier metal is formed, it is desirable to polish the barrier metal together with the wiring metal by a single polishing process. However, the wiring metal layer is mainly polished. In some cases, polishing is performed in a plurality of stages including a step of performing (primary polishing) and a step of polishing wiring metal together with the barrier metal (secondary polishing). Therefore, the polishing slurry may be changed and adjusted between the previous polishing and the subsequent polishing. More specifically, since the polishing rate is different between the wiring metal and the barrier metal, the polishing slurry mainly used for polishing and removing the wiring metal and the polishing slurry mainly used for polishing the barrier metal are used for polishing. A slurry was prepared, and a polishing operation was carried out using different polishing slurries according to each step.
したがって、研磨用スラリーの変更など工程変更に要する時間が必要となり、研磨作業の効率は低いものとなっていた。 Therefore, the time required for the process change such as the change of the polishing slurry is required, and the efficiency of the polishing work is low.
本発明は、性質の異なる複数の研磨対象を同時に研磨する場合のように、従来複数の研磨工程を必要としていた研磨作業において、一度の研磨作業によって所望の研磨を短時間で行うことができ、研磨作業の効率を高めることのできる研磨用スラリーの提供を解決しようとする課題としている。 The present invention can perform desired polishing in a short time by a single polishing operation in a polishing operation that conventionally required a plurality of polishing steps, such as when simultaneously polishing a plurality of polishing objects having different properties, An object of the present invention is to provide a polishing slurry that can increase the efficiency of the polishing operation.
本発明による研磨用スラリーは、研磨砥粒と、少なくとも２種以上の異なる酸化剤とを含有することを特徴とするものである。 The polishing slurry according to the present invention is characterized by containing abrasive grains and at least two or more different oxidizing agents.
本発明の研磨用スラリーによれば、複数の金属層を有する研磨対象物に対しての研磨において、上記異なる酸化剤に対応してそれぞれの金属層を高い研磨レートで研磨することができるので、従来のごとく金属層毎に研磨工程を分けて研磨する必要がなくて済み、研磨工程数の削減が可能となるうえ研磨時間も短くて済み、高い効率での研磨作業が可能となる。 According to the polishing slurry of the present invention, in polishing against a polishing object having a plurality of metal layers, each metal layer can be polished at a high polishing rate corresponding to the different oxidizing agents, Unlike the conventional method, it is not necessary to divide the polishing process for each metal layer, so that the number of polishing processes can be reduced and the polishing time can be shortened, and a highly efficient polishing operation can be performed.
上記研磨砥粒はシリカ系、特に非真球状のコロイダルシリカ０．０１〜１０重量％含有していることが好ましい。非真球状のコロイダルシリカを用いることによって、被研磨面への傷などを抑制した状態で良好な研磨が行える。 The abrasive grains preferably contain 0.01 to 10% by weight of silica-based, particularly non-spherical colloidal silica. By using non-spherical colloidal silica, good polishing can be performed in a state where scratches on the surface to be polished are suppressed.
上記酸化剤は、過酸化化合物と、非過酸化化合物とを含み、その非過酸化化合物は、ヨウ素酸塩化合物、塩素酸塩化合物、硫黄化合物からなる群の中から選択された少なくとも１種以上であることが好ましい。この場合、過酸化化合物が特にバリア金属に対する酸化剤として有効に機能し、研磨レートを高いものにでき、作業効率を向上できる。 The oxidizing agent includes a peroxide compound and a non-peroxide compound, and the non-peroxide compound is at least one selected from the group consisting of an iodate compound, a chlorate compound, and a sulfur compound. It is preferable that In this case, the peroxide compound functions effectively as an oxidizing agent for the barrier metal, and the polishing rate can be increased, thereby improving the working efficiency.
酸化剤全体の濃度は、０．０１〜２０重量％、特に、０．０１〜１０重量％が好ましい。 The concentration of the entire oxidizing agent is preferably 0.01 to 20% by weight, and particularly preferably 0.01 to 10% by weight.
特に、０．０１〜２０重量％の有機酸を含むことが好ましい。 In particular, it is preferable to contain 0.01 to 20% by weight of an organic acid.
本発明によれば、複数の金属層を有する研磨対象物に対しての研磨において、金属層毎に研磨工程を分けて研磨する必要がなくて済み、研磨工程数の削減が可能となるうえ研磨時間も短くて済み、高い効率での研磨作業が可能となる。 According to the present invention, it is not necessary to separate the polishing process for each metal layer in the polishing of the polishing object having a plurality of metal layers, and the number of polishing processes can be reduced and the polishing can be performed. The time can be shortened and the polishing operation can be performed with high efficiency.
本発明のこの実施の形態に係る研磨用スラリーは、純水等の水系媒体と、研磨砥粒として、非真球状のコロイダルシリカと、２種の酸化剤と、有機酸とを含有している。これら各成分の好ましい配合割合は、１００重量部の純水に対して、コロイダルシリカが０．１〜２０重量部、酸化剤全体が０．１〜２０重量部、有機酸が０．１〜１０重量部である。さらに好ましくは、１００重量部の純水に対して、コロイダルシリカが０．１〜１０重量部、酸化剤全体が０．１〜１０重量部、有機酸が０．１〜５重量部である。 The polishing slurry according to this embodiment of the present invention contains an aqueous medium such as pure water, and non-spherical colloidal silica, two kinds of oxidizing agents, and an organic acid as polishing abrasive grains. . The preferred blending ratios of these components are 0.1 to 20 parts by weight of colloidal silica, 0.1 to 20 parts by weight of the entire oxidizing agent, and 0.1 to 10 parts of organic acid with respect to 100 parts by weight of pure water. Parts by weight. More preferably, the colloidal silica is 0.1 to 10 parts by weight, the entire oxidizing agent is 0.1 to 10 parts by weight, and the organic acid is 0.1 to 5 parts by weight with respect to 100 parts by weight of pure water.
なお、研磨用スラリーには、分散剤や、界面活性剤など各種添加剤が含有されることがある。 The polishing slurry may contain various additives such as a dispersant and a surfactant.
酸化剤としては、第１の酸化剤と第２の酸化剤との２種があり、具体例として、第１の酸化剤としては、非過酸化化合物（非過酸化物）であるヨウ素酸カリウム（ＫＩＯ３）であり、第２の酸化剤は、過酸化化合物（過酸化物）である過酸化水素（Ｈ２Ｏ２）である。 There are two types of oxidizing agents, a first oxidizing agent and a second oxidizing agent. As a specific example, as the first oxidizing agent, potassium iodate, which is a non-peroxide compound (non-peroxide), is used. (KIO 3 ), and the second oxidizing agent is hydrogen peroxide (H 2 O 2 ), which is a peroxide compound (peroxide).
なお、本発明の研磨用スラリーでは、酸化剤としては、２種以上の異なる種類の酸化剤が混合されたものであればよい。 In the polishing slurry of the present invention, the oxidizing agent may be any mixture of two or more different types of oxidizing agents.
酸化剤の具体例としては、上述のヨウ素酸カリウムや、過酸化水素のほかに、以下のようなものが挙げられる。 Specific examples of the oxidizing agent include the following in addition to the above-mentioned potassium iodate and hydrogen peroxide.
第１の酸化剤は、ヨウ素酸塩化合物、塩素酸塩化合物、硫黄化合物から選択された少なくとも１種以上の非過酸化化合物である。 The first oxidizing agent is at least one non-peroxidized compound selected from an iodate compound, a chlorate compound, and a sulfur compound.
このヨウ素酸塩化合物としては、ヨウ素酸カリウム、ヨウ素酸ナトリウムがあり、塩素酸塩化合物としては、塩素酸カリウム、塩素酸ナトリウム、塩素酸カルシウムがあり、硫黄化合物としては、硫酸アンモニウムがある。 Examples of the iodate compound include potassium iodate and sodium iodate. Examples of the chlorate compound include potassium chlorate, sodium chlorate, and calcium chlorate. Examples of the sulfur compound include ammonium sulfate.
第２の酸化物は、過酸化化合物であり、この過酸化化合物として、過酸化水素の他に、過塩素酸アンモニウム、過塩素酸カリウム、過塩素酸ナトリウム、過ヨウ素酸アンモニウム、過マンガン酸ナトリウム、過マンガン酸カリウムなどがある。 The second oxide is a peroxide compound. As the peroxide compound, in addition to hydrogen peroxide, ammonium perchlorate, potassium perchlorate, sodium perchlorate, ammonium periodate, sodium permanganate And potassium permanganate.
なお、研磨用スラリー中における酸化剤全体の濃度は、０．０１〜２０重量％であることが好ましい。酸化剤の濃度が０．０１重量％よりも小さいと、化学研磨としての機能が十分でなく、研磨レートが研磨作業上低くなり過ぎる。また、酸化剤の濃度が２０重量％よりも大きいと、研磨レートが高くなり過ぎて、研磨作業の良好な制御が難しいものとなる。 In addition, it is preferable that the density | concentration of the whole oxidizing agent in the slurry for polishing is 0.01 to 20 weight%. When the concentration of the oxidizing agent is less than 0.01% by weight, the function as chemical polishing is not sufficient, and the polishing rate becomes too low for the polishing operation. On the other hand, if the concentration of the oxidizing agent is higher than 20% by weight, the polishing rate becomes too high, and it becomes difficult to control the polishing operation well.
さらに、既存の研磨用スラリーのｐＨが２であることを考慮し、かつ、第２酸化剤として用いた過酸化水素の安定性を高めるため、上述したように有機酸が添加されている。この場合、有機酸としては、マロン酸を２．０重量％添加している。マロン酸以外にも、例えば、乳酸、酢酸、蟻酸、ニコチン酸、リンゴ酸、クエン酸、サリチル酸、アジピン酸、コハク酸、マレイン酸、酒石酸、アスコルビン酸、キナルジン酸、吉草酸、酪酸、没食子酸、アミノ酸などを用いてもよい。特にカルボン酸基を含む有機化合物であることが好ましい。この有機酸はｐＨ緩衝剤として機能する。 Further, in consideration of the fact that the pH of the existing polishing slurry is 2, and in order to improve the stability of hydrogen peroxide used as the second oxidizing agent, an organic acid is added as described above. In this case, 2.0% by weight of malonic acid is added as the organic acid. In addition to malonic acid, for example, lactic acid, acetic acid, formic acid, nicotinic acid, malic acid, citric acid, salicylic acid, adipic acid, succinic acid, maleic acid, tartaric acid, ascorbic acid, quinaldic acid, valeric acid, butyric acid, gallic acid, An amino acid or the like may be used. In particular, an organic compound containing a carboxylic acid group is preferable. This organic acid functions as a pH buffer.
特に、マロン酸の場合、研磨用スラリーのｐＨを２近くに調整するのに適しているとともに、第１の酸化剤としてヨウ素酸カリウムを用いた場合、そのヨウ素酸カリウムによる研磨用スラリーの発色を抑制する作用がある。 In particular, in the case of malonic acid, it is suitable for adjusting the pH of the polishing slurry to be close to 2, and when potassium iodate is used as the first oxidizing agent, the coloring of the polishing slurry by the potassium iodate is developed. There is an inhibitory effect.
なお、研磨用スラリー中における有機酸の濃度は、０．０１〜２０重量％であることが好ましい。研磨用スラリー中における有機酸の濃度が０．０１重量％よりも小さいと、例えばｐＨが２に調節できないという問題点がある。研磨用スラリー中における有機酸の濃度が２０％よりも大きいと、スラリーが強酸になり、粒子が凝集するという問題点がある。 The concentration of the organic acid in the polishing slurry is preferably 0.01 to 20% by weight. If the concentration of the organic acid in the polishing slurry is less than 0.01% by weight, there is a problem that the pH cannot be adjusted to 2, for example. When the concentration of the organic acid in the polishing slurry is higher than 20%, there is a problem that the slurry becomes a strong acid and the particles are aggregated.
非真球状コロイダルシリカは、テトラメトキシシラン等の有機ケイ素化合物を原料としたゾルゲル法（加水分解法）で作製されたものを用いることができる。なお、非真球状コロイダルシリカのサイズは、短径が３０〜８０ｎｍで、長径／短径比が１．０〜１．８であることが好ましい。また、非真球状のコロイダルシリカの研磨用スラリー中における含有率は、０．０１〜１０重量％であることが好ましい。研磨用スラリー中における非真球状のコロイダルシリカの含有率が０．０１重量％よりも小さいと、機械的な研磨能力が低下するという問題点がある。研磨用スラリー中における非真球状のコロイダルシリカの含有率が１０％よりも大きいと、機械的な研磨能力が増大してディッシング量やエロージョン量が高くなるという問題点がある。 As the non-spherical colloidal silica, one produced by a sol-gel method (hydrolysis method) using an organic silicon compound such as tetramethoxysilane as a raw material can be used. The non-spherical colloidal silica preferably has a minor axis of 30 to 80 nm and a major axis / minor axis ratio of 1.0 to 1.8. The content of non-spherical colloidal silica in the polishing slurry is preferably 0.01 to 10% by weight. When the content of non-spherical colloidal silica in the polishing slurry is less than 0.01% by weight, there is a problem that the mechanical polishing ability is lowered. If the content of non-spherical colloidal silica in the polishing slurry is larger than 10%, there is a problem that the mechanical polishing ability increases and the dishing amount and erosion amount increase.
研磨用スラリーの水系媒体としては、水、エタノール、メタノール等、およびこれらの混合溶媒が使用できるが、好ましくは脱イオンされた純水である。
この研磨用スラリーを用いてタングステン、窒化チタン、チタン、ＴＥＯＳ膜に対して研磨することができた。
As an aqueous medium for the polishing slurry, water, ethanol, methanol, or a mixed solvent thereof can be used, and deionized pure water is preferable.
Using this polishing slurry, it was possible to polish tungsten, titanium nitride, titanium, and TEOS films.
本発明に係る研磨用スラリーとして、純水８９重量％に対して、第１の酸化剤としてヨウ素酸カリウムを３．０重量％、第２の酸化剤として過酸化水素を４．５重量％、有機酸としてマロン酸を２．０重量％を混合し、攪拌分散して研磨用スラリーを作製した。 As a polishing slurry according to the present invention, potassium iodate is 3.0% by weight as a first oxidant and hydrogen peroxide is 4.5% by weight as a second oxidant with respect to 89% by weight of pure water. As an organic acid, 2.0% by weight of malonic acid was mixed and stirred and dispersed to prepare a polishing slurry.
タングステン（Ｗ）膜、窒化チタン（ＴｉＮ）膜、チタン（Ｔｉ）膜、ＴＥＯＳ（テトラエトキシシラン）膜をそれぞれ表面に形成したウェハを研磨試料として用意し、それぞれのウェハについて上記作製された研磨用スラリーにて研磨し、それぞれの膜について研磨レート（研磨速度）を測定し、その結果を図１のグラフに示している。また、その研磨の比較を行うため、重量％に対して、酸化剤としてヨウ素酸カリウムを３．０重量％のみ含有し、有機酸として乳酸を６．５４重量％を混合し、攪拌分散して作製した研磨用スラリーについても、上記各研磨試料を研磨する実験を行った。なお、この実験については、研磨装置は、ＳｐｅｅｄＦａｍ−ＩＰＥＣ社製のＡＶＡＮＴＩ４７２を用いた。研磨圧力は、５ｐｓｉ、定盤回転数は１００ｒｐｍ、キャリア回転数は９４ｒｐｍ、スラリー流量は、１７０ｍｌ／ｍｉｎ、研磨時間は１ｍｉｎとした。また、パッドは、Ｒｏｄｅｌ−Ｎｉｔｔａ社製ＩＣ１４００ ｋ−ｇｒｏｏｖｅを用いた。 A wafer having a tungsten (W) film, a titanium nitride (TiN) film, a titanium (Ti) film, and a TEOS (tetraethoxysilane) film formed on the surface is prepared as a polishing sample, and the above-prepared polishing wafer is prepared for each wafer. Polishing with a slurry and measuring the polishing rate (polishing rate) for each film are shown in the graph of FIG. In order to compare the polishing, the mixture contains only 3.0% by weight of potassium iodate as an oxidizing agent and 6.54% by weight of lactic acid as an organic acid, and is stirred and dispersed. An experiment for polishing each of the above polishing samples was also conducted on the prepared polishing slurry. In this experiment, AVANTI472 manufactured by SpeedFam-IPEC was used as the polishing apparatus. The polishing pressure was 5 psi, the platen rotation speed was 100 rpm, the carrier rotation speed was 94 rpm, the slurry flow rate was 170 ml / min, and the polishing time was 1 min. Moreover, IC1400 k-groove made from Rodel-Nitta was used as the pad.
研磨レートの測定は、ＴＥＯＳ膜に対してはＮＡＮＯＭＥＴＲＩＣＳ社製のＮａｎｏｓｐｅｃ／ＡＦＴ５１００を、Ｗ、Ｔｉ、ＴｉＮ膜に対してはＰｒｏｍｅｔｒｉｘ社製のＯｍｎｉＭａｐ ＲＳ３５Ｃを用いて複数点測定し、その平均を算出することで行なった。 The polishing rate is measured by using NANOMETRICS Nanospec / AFT5100 for TEOS film, and Prometrix OmniMap RS35C for W, Ti and TiN films, and calculating the average. It was done.
本発明に係る研磨用スラリーと比較例の研磨用スラリーとについて、その研磨レートの測定結果について、図１に基づいて説明する。 With respect to the polishing slurry according to the present invention and the polishing slurry of the comparative example, the measurement results of the polishing rate will be described with reference to FIG.
タングステンについての本発明に係る研磨用スラリーによる研磨レートは、３０４３（Å／ｍｉｎ）であり、比較例の研磨用スラリーによる研磨レートは、２４８２（Å／ｍｉｎ）である。窒化チタンについての本発明に係る研磨用スラリーによる研磨レートは、２４７４（Å／ｍｉｎ）であり、比較例の研磨用スラリーによる研磨レートは、２０５３（Å／ｍｉｎ）である。チタンについての本発明に係る研磨用スラリーによる研磨レートは、１４６１（Å／ｍｉｎ）であり、比較例の研磨用スラリーによる研磨レートは、９４９（Å／ｍｉｎ）である。ＴＥＯＳについての本発明に係る研磨用スラリーによる研磨レートは、６７（Å／ｍｉｎ）であり、比較例の研磨用スラリーによる研磨レートは、５５（Å／ｍｉｎ）である。 The polishing rate with the polishing slurry according to the present invention for tungsten is 3043 (Å / min), and the polishing rate with the polishing slurry of the comparative example is 2482 (Å / min). The polishing rate with the polishing slurry according to the present invention for titanium nitride is 2474 (Å / min), and the polishing rate with the polishing slurry of the comparative example is 2053 (Å / min). The polishing rate with the polishing slurry according to the present invention for titanium is 1461 (Å / min), and the polishing rate with the polishing slurry of the comparative example is 949 (Å / min). The polishing rate by the polishing slurry according to the present invention for TEOS is 67 (Å / min), and the polishing rate by the polishing slurry of the comparative example is 55 (Å / min).
この結果、タングステン膜については、比較例と比して本発明の研磨用スラリーでは、研磨レートが２３％高いものとなり、窒化チタン膜については、同じく２１％高いものとなり、チタン膜については、同じく５４％高いものとなった。 As a result, for the tungsten film, the polishing slurry of the present invention has a polishing rate of 23% higher than that of the comparative example, the titanium nitride film is also 21% higher, and the titanium film is the same. 54% higher.
上記実施の形態で示した本発明は、一例であって、例えば次のような変形例や応用例も考えられる。 The present invention described in the above embodiment is an example, and for example, the following modifications and application examples are also conceivable.
（１）上記実施の形態では、研磨用スラリーに含まれる砥粒としてシリカ系の非真球状コロイダルシリカを用いたが、例えばフュームドシリカなどを用いてもよい。 (1) In the above embodiment, silica-based non-spherical colloidal silica is used as the abrasive grains contained in the polishing slurry, but fumed silica or the like may be used, for example.
（２）上記実施の形態では、本発明に係る研磨用スラリー中に２種の異なる酸化剤を含ませたものを示したが、３種以上の異なる酸化剤を含ませた研磨用スラリーであってもよい。 (2) In the above embodiment, the polishing slurry according to the present invention includes two different oxidizing agents, but the polishing slurry includes three or more different oxidizing agents. May be.
本発明は、半導体、電子部品の製造工程で使用される研磨用スラリーに関し、例えば、各種の半導体製造過程における基板の薄膜などを研磨するのに供される研磨用スラリーに利用可能である。 The present invention relates to a polishing slurry used in a manufacturing process of a semiconductor or an electronic component, and can be used, for example, as a polishing slurry used for polishing a thin film of a substrate in various semiconductor manufacturing processes.
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| JP2006297501A (en) * | 2005-04-15 | 2006-11-02 | Hitachi Chem Co Ltd | Polishing material and polishing method of composite material composed of magnetic metal film and insulating material film |
| JP2007048908A (en) * | 2005-08-09 | 2007-02-22 | Nitta Haas Inc | Polishing composition |
| WO2007026863A1 (en) * | 2005-09-02 | 2007-03-08 | Fujimi Incorporated | Polishing method |
| JP2007194593A (en) * | 2005-12-20 | 2007-08-02 | Fujifilm Corp | Polishing liquid for metal and polishing method using the same |
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| JPWO2008117593A1 (en) * | 2007-03-26 | 2010-07-15 | Jsr株式会社 | Chemical mechanical polishing aqueous dispersion and semiconductor device chemical mechanical polishing method |
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| JP2020010029A (en) * | 2018-07-03 | 2020-01-16 | ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド | Neutral to alkaline chemical mechanical polishing compositions and methods for tungsten |
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| JP2006297501A (en) * | 2005-04-15 | 2006-11-02 | Hitachi Chem Co Ltd | Polishing material and polishing method of composite material composed of magnetic metal film and insulating material film |
| JP4635694B2 (en) * | 2005-04-15 | 2011-02-23 | 日立化成工業株式会社 | Polishing material and polishing method for polishing a composite film including a magnetic metal film and an insulating material film |
| JP2007048908A (en) * | 2005-08-09 | 2007-02-22 | Nitta Haas Inc | Polishing composition |
| JP4708911B2 (en) * | 2005-08-09 | 2011-06-22 | ニッタ・ハース株式会社 | Polishing composition |
| WO2007026863A1 (en) * | 2005-09-02 | 2007-03-08 | Fujimi Incorporated | Polishing method |
| JP2007194593A (en) * | 2005-12-20 | 2007-08-02 | Fujifilm Corp | Polishing liquid for metal and polishing method using the same |
| JPWO2008117593A1 (en) * | 2007-03-26 | 2010-07-15 | Jsr株式会社 | Chemical mechanical polishing aqueous dispersion and semiconductor device chemical mechanical polishing method |
| JP5403262B2 (en) * | 2007-03-26 | 2014-01-29 | Ｊｓｒ株式会社 | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method for semiconductor device |
| JP2010005704A (en) * | 2008-06-24 | 2010-01-14 | Jsr Corp | Chemical mechanical polishing water-based dispersing composition for polishing barrier metal layer provided on substrate for use of display device, its manufacturing method, and method of chemical mechanical polishing |
| JP2010010167A (en) * | 2008-06-24 | 2010-01-14 | Jsr Corp | Aqueous dispersion for chemical mechanical polishing, method of manufacturing aqueous dispersion for chemical mechanical polishing, and method for chemical mechanical polishing |
| JP2020010029A (en) * | 2018-07-03 | 2020-01-16 | ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド | Neutral to alkaline chemical mechanical polishing compositions and methods for tungsten |
| JP7420493B2 (en) | 2018-07-03 | 2024-01-23 | ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド | Neutral to alkaline chemical mechanical polishing composition and method for tungsten |
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